Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



PROCESS FOR BREG PET-RGLEUM EMUL- SIONS ELOYING CERTAm :POLYEPOLXHDE TREATED DERIVATIVES OBTAINED 'BYREAC- TION OF MGNOEPOXIDES WiTZ-i RESINS Melvin De Groote, University City,-and Kwan-Ting Sheri, Brentwood, Mm, assignors to-Petroiite (Iorporation, Wilmington, Del.,'a corporation of Delaware No Drawing. Application Iiune 1i),- 1%3, Serial No. 360,845

20 Claims. (CL 252344) The present invention is a continuation inepart of our co-pending application, Serial No. 350,535, filed AprillZZ, 1953, now Patent No. 2,771,434.

Our invention provides an economical and rapid Process for resolving petroleum emulsions of the water-inoil type that are commonly referred toas fcnt oil, ,r'oily oil, emulsified oil, etc., and which comprisefinedroplets of naturally-occurring waters or hrines dispersed in a more or less permanent state throughouttheoil which constitutes the continuous phase of theinvention.

It also provides an economical and rapid process for separating emulsions whichhave been prepared under controlled conditions from mineral oil, tsuchiascrude oil and relatively soft waters or weak brines. vControlled emulsification and subsequent demulsification.under-the conditions just mentioned are of significant yaluein removing impurities, particularly, inorganic salts, from ,pipeline oil.

The present invention is concerned withthe breaking of emulsions of the water-in-oil type by ,s-ubjectingthem to the action of products obtained bya B-stepmanufacturing process involving (1) condensing certaimphenol aldehyde resins, hereinafter described. in detail,. withicertain cyclic amidines, hereinafter describedin, detail, and formaldehyde; (2) oxyalkylation of .;the. condensation product with certain monoepoxides, hereinafterdescribed in detail; and (3) oxyalkylation .of the previouslyoxyalkylated resin condensate withcertaintnon-aryl,hydrophile polyepoxides, also hereinafter described in, detail.

The present invention is characterized by vthe,,.use-of compounds derived fromdiglycidyl ethe-rs which. do not introduce any hydrophobe properties-in its usual meaning but in fact are more aptto introduce hydrophile properties. Thus, the diepoxides employed in the presentinvention are characterized by the fact that .the divalent radical connecting the terminal epoxideradicals. :c ontains less than 5 carbon atoms in any uninterruptedchain.

The diepoxides employed in the presentprocess are obtained from glycols such as ethylene glycol, .diethyien: glycol, propylene glycol,dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, andtsimilar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which isypart of the radical joining the epoxide groups. Ofwnecessity; such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, 'Serial- No. 350,535, are invariably and inevitably aryl in character.

The diepoxides employed in that present process; are usually obtained by reacting a glycol or equivalent .compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides ketones, esters, ethers, mixed solvents, etc. 10

the 1,2 -epoxy ring. has two or more oxirane rings they will be referred to as --polyepoxides. They usually represent, of course, 1,2- 30,.

have been described in the literature and particularly the patent literature.

Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below tthe point of pyrolysis and thus differentiates them from .infusible resins. Reference to being soluble inan organic solvent means any of the usual organic solvents such as alcohols, Reference tosolubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. far tha-t it sometimes is desirable to dilutethe compound containing the epoxy rings before reacting with an oxy- "alkylated amine condensate. In such instances, of course, the solvent selected would have to be one which is not Furthermore, solubilityis a factor insosusceptible to oxyalkylation, as, for example, kerosene,

w benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethylene- 20- glycol -diethylether, diethyleneglyc-ol diethylether, and

dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to;the 1,2-epoxy ring. The 1,2-epoxy ringtissometimesreferred to-as theoxi-rane ring to distinguish it from other epoxy rings. iiereinafter the word epoxy unless indicated otherwise, will be used tomean the oxirane ring, i. e., Furthermore, where a compound epoxide rings or oxirane rings in the alpha-omega position. This is a departure from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxidewhich contains at least 4 carbon atoms and is formally described as l,2-epoxy-3,4-epoxybutane(1,2-3,4 diep oxybutane) It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product-described in'the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecularweight, have been described as complex resin- .ous-epoxides which are polyether derivatives of polyhydric compounds containing an averageof more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. -The compounds here included are limited to the, monomers or the low molal members of such series and generally containttwo epoxide rings per molecule and maybe entirely free from a hydroxyl group. the-instant invention is directed towards products which This is important because are not insoluble resins and have certain solubility char- ;acteristics not inherent in theusual thermosetting resins.

Simply for purpose of illustration to show a typical diglycidyl ether of the kind herein employed reference is made-t0 the following formula:

orifderived from cyclic diglycerol the structure would :beithuS:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

HQ'LH H HCO-CH HC-O-CH HCH I Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained an acyclic reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any oxyalkylated phenolaldehyde resin condensate by virtue of the fact that there are always present eitherphenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondary amino group.. In any event there is always a multiplicity of reactive hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will'be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having 2 oxirane rings and an oxy-.

alkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the oxyalkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which n is a small whole number less than 10, and

usually less than 4, and including 0, and R1 represents.

a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization oxyalkylated condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water contalnmg an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base f such reactions.

of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or parts of xylene and 30 parts of methanol, can be used. Sometimes it is desir-- able to add a small amount of acetone to the xylenemethanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e... combination with water or particularly in the form of alow molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufliciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Grooteet al. In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be Xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethyl ether, or a low molal alcohol, or a mixture-to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. 7' Such test is ob-- viously the same'for the reason that there will'be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 3 is concerned with appropriate basic cyclic amidines which may be employed in the preparation of the herein-described amine-modified resins;

Part 4 is concerned with reactions involving theresin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides;

Part 5 is concerned with the oxyallrylation of the products described in Part 4, preceding;

Part 6is concerned with reactions involving the two preceding types of materials and examples obtained by Generally speaking, this involves nothing more than a reaction between two moles of a previously-prepared oxyalkylated amine-modified phenolaldehyde resin condensate as described and one mole of (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

i 7 PART 1 Reference is made to various patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as' reactants in the instant invent-ion. More specifically, such patents are the following: Italian Patent No. 400,973, dated August-8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No."2,070,990, dated February 16, 1 937, toGroll et al.; and U. S. Patent No. 2,581,464,

dated January 8-, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene: Such: derivatives are obtained by the use of peroxides or by other suitablelmeans andl the: diglycidyl ethers may be indicated thus;

in some instances the compounds,areessentially derivatives of etherized. epichlorohydrin, or methyl epichloro hydrin; Needlessto say, suchcompounds can be derived fromglycerolmonochlorohydrin by etherization prior to ring closure; An example is illustrated in the previously mentioned Italiam Patent No. 400,973

Another typeofudiepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and. is. of thefollowing formula,

0. HzC- (l)CHzCHzO CHi CH; CH: .The diepoxides previously described may bevindicated by the. following formula:

H R R! H HC-C-R -o-cH in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral or 1. As previously pointed out,,in the case of the butadiene derivative, 11 is 0. In the case of diisobutenyl dioxide R is CH2CH2 and n' is 1. In another example previously referred to R is CH2OCH2 and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin, Thisparticular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings, As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented, the formula becomes:

In the above formula R1 is selected from groups such as the following:

is derived actually or theoretically, or at least derivable,

from the diol, HOROH, in which the oxygen-linked hydrogen atoms were. replaced by H H H -c-0-0 H Thus, R.(,QH,),11,,, where n represents a small whole number which is, 2, or more, must bewater-soluble.v Such limitationexcludes polyepoxides if actually derived or theoretically derived. at. least, from water-insoluble diols or Water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.-

Referring to a compound of the; type above in the formula H H H H H H C-CGO[R1]OCCCH H H inwhich Rr is C3H5(OH) it is obvious that reaction with another mole of epichlorohydrin withappropriate ring closure-would produce a triepoxide or, similarly, if R happened to be CsH5(OI-I) OC3H5(OH), one could obtain a tetraepox-ide. Actually, such procedure generaliy yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which di epoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl' ether, or, stated another way, it can be considered as being formed from one mole of diglyeero-l' and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per, molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyil ether is used, although obviously any of the others previously described would be just as suitable; For convenience, this diepoxide will be referred to as, diglyoidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethy1- eneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only; For this reason, the subsequent table referring tothe'use of this particular diepoxide, which will: be referred toas diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology tor. these polyepoxides, and particularly diepoxide s, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom, and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a'heterocyclicring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic' ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula .0H OH OH R R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instanceof low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from'any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance, paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,368, or in U. S. Patent No. 2,499,368, dated'March 7, 1950, to De Groote and'Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei'per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity are'derived by reaction between a difunctional monohydric phenol and .an aldehyde having not'over-8 carbonatoms and'reactive toward said phenol and are formed in' thesubstantial absence of' trifunctional phc' nols. The phenol is of the formula R R n R In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all," 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously,- as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form th'ejresin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture. 1

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other Words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The

asses-er 9 amount may be as small as a 200th of a percent and as much as a few 10ths ofia percent. Sometimes moderate increase in caustic sodaandcaustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins. onedoesnot. getaa single polymer, 1. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It-is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to .a fractional value for n' as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture oftlieresins we found no reason for using other than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE. I

M01. wt. Ex- Position R" of resin ample R of R derived 1: molecule number from- (based on n+2) 1a Phenyl Para. Formal- 3. 5 992. 5

dehyde. I Tertlary'butyl; i 3.5 882. 5 Secondary bntyl 3. 5 882. 5 Cyclo-hexyl 3. 5 1, 025. 5 Tertiary amyl. 3. 5 f) .5 Mixed second 3. 5 805. 5

and tertiarya-myl. Propyl 3. 5 805. 5 Tertiary hexyl 3. 5 1, 036. 5 Octyl 3. 5 1, 190. 5 NonyL. 3. 5 1, 267. 5 DecyL 3. 5 1, 344. 5 Dodecyl 3.5 1, 498.5 Terti ry butyl 3. 5 945. 5

Tertiary-211113 1- 1 3. 5 1, 14B. 5 onyl do 3. 5 1, 456. 5 Tertiary butyl Propion- 3. 5 1, 008. 5

aldehyde. Tertiary amyl o 3. 5 1, 085.5 Nonyl do- 3. 5 1, 393. 5 Tertiary butyl Formal- 4. 2 996. 6

2. 0 602.0 Hexyl. 2.0 748. 0 Oyclo-hexyl 2. 0 740. 0

PART 3 The expressionfcyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms. completing the ring. All the carbon atoms may be substituted. The nitrogen atom of the ring involving. twomonovalent' linkages may be substituted. Needless to say, these compounds include members in which the substituents also may have one or more nitrogen atoms, either in the form of amino nitrogen atoms or in the form of acylated nitrogen atoms.

--These cyclic amidines'are sometimes characterized as being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of thering'is generally 10 bonded to ahydrocar-bon radical or comparable radical derived'from- 8.11.21Cid, such as a low rnolal fatty acid, a high molal fattyacid', or comparable acids such as polycnrboxy acids.

Cyclic amidinesobmined from: oxidizcdawax acids: are described in detail in co pending Blair application, Serial No. 274,075, filed February 28, 1952'. Instead of being derived from oxidized" wax acids; thecyclic compounds liereinemployed may be obtained from any' acid from acetic acid' upward, and-may" be obt'ainetlfrom: acids, such as benzoic, or acidsin which there is a reoccurring. ether linkage in the acyl radical. In essence then, with this difference said aforementioned co-pending Blair application, Serial No. 274,075, describe compounds of the following structure:

where Rrepresents hydroearbonradicals having up'to ap' proximately 30 carbon atoms and includes hydroxylated hydrocarbon radicals and also hydrocarbon radicals in which the carbon atom chain is interrupted by oxygen; n is the numeral 2 to 3, E re resentshydrogen and organic radicals containing less than 25- carbon atoms, composed of the elements including C, N,'() and H, and B represents hydrogen and hydrocarbon radicals containing less than 7 carbon atoms, with the proviso that at least three occurrences of B are hydrogen.

The preparation ofarr'imidazoline substituted in the two-position by lower aliphatic hydrocarbon radicals is described inthe literature. and is readily carried out. by reaction between a monocarboxylic acid or' ester or. amide and a diamine or polyarnine, containing at least one primary amino group, and at least one. secondary amino group or a second primary amino group separated from the first primary amino group by two carbon atoms.

Examples of suitable polyamines which can be employed as reactants to form basic nitrogen-containing compounds of the present invention include polyalkylene polyamines such asethylene-diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and higher polyethylene polyamines, and also including 1,2-diaminopropane, N-ethylethylenediarnine, N,N-dibutyldiethylenetriamine, 1,2 diaminobutane, hydroxyethylethylenediamine,1,2-propylenetriamine, and. the like.

For details of the preparation of imidazolines substituted in the Z-positionfrom amines of this type, see the following U. S. patents: U. S. No. 1,999,989, dated April. 30, 1935, MaxiBockr-nuhlet al.; U. S..N'o. 2,155,877, dated April 25, 1939, Edmund Waldmann et al.; and U. S. 2,155,878; dated April. 25, 1939, Edmund Waldmann et 8.1. Also seeChem. Rev., 32, 47 (.43).

Equally suitable for. use in preparing compounds of my invention and for'the preparation oftetrahydropyrimidines substituted inthe 2-position are the polyamines con: taining at leastoneprimary amino-group and at least one secondary amino. group, or another primary amino group separated from the first primary amino group by three carbon atoms- This reaction is generally carried out by heating the reactants to a temperature of 230 C. or higher, usually within the range of 250 C. to 300 C., at which temperatures water is evolved and ring closure is eifected. For details. of the preparation of tetrahydropyrimidines, see German Patent No. 700,371, dated December 18, 1940, to Edmund Waldrnann and August Chwala; German Patent No. 701,322, dated January 14, 1941, to Karl Miescher, Ernst Erech and Willi Klarer; and U. S. Patent No. 2,194,419, dated March 19, 1940, to August Chwala.

Examples of amine, suitable for this synthesis include 1,3-propylenediamine, trim'ethylenediamine, 1,3-diaminobutane, 2,4-diaminopentane, N-ethyl trimethylenediamine,

N-aminoethyltrimethylene diamine, aminopropyl stearylamine, tripropylenetetramine, tctrapropylenepentamine, high boiling polyamines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyamines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

From a practical standpoint, as will be explained hereinafter, the polyethylene imidazolines are most readily available and most economical for use. Thus, broadly speaking, the present invention is concerned with a condensation reaction, in which one class of reactants are substituted ring compounds 16 N\ N\ N\ N R-C R R0 R' 11-0: /R R-O 3 N l t r R" IB'R" YR" 20 in which R is a divalent alkylene radical of the class of CH:CH2- CHzCH2CH:

H CCH:-

and in which D' represents a divalent, non-amine, organic radical containing less than 25 carbon atoms, composed of elements including C, H, O, and n; Y represents a divalent, organic radical containing less than 25 carbon atoms, composed of elements including C, H, O, and N, and containing at least one amino group, and R represents hydrogen, aliphatic hydrocarbon radicals, hydroXyl- 40 ated aliphatic hydrocarbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cycloaliphatic hydrocarbon radicals; R" represents hydrogen, aliphatic radicals and cycloaliphatic radicals.

As to the six-membered ring compounds generally referred to as substituted pyrimidines, and more particularly as substituted tetra-hydropyrimidines, see U. S. Patent No. 2,534,828, dated December 19, 1950, to Mitchell et al. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of the five-membered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned U. S. Patent No. 2,534,828.

For purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations: '(a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two-ring membered radicals present instead of one ring-membered radical and may or may not have present a tertiary amino radical or a hydroxyl radical, such as a hydroxy alkyl radical. A large number of compounds have been described in the literature meeting the above specifications, of which quite a fewappear in the aforementioned issued U. S. patents. Examples se lected from the patents include the following:

N-CH: I

Cn zz- V V N-C H: 1!! 2-undecylimidazollne r a (Julia. 0

N CH2 7 2 4.NE. C iuHn 1-N-decylaminoethyl,2-ethyllmidazo1ine /NCH2 CHLC CzH4.NH. C2H4.N H. CruHu 2-methyl,l-hexadecylaminoethylaminoethylimidazoline N-C n, H. O

NC H1 Ha.NH. C 12H" 1-dodecylaminopropylimidazollne N-CH: H. (1

NCHa )zH;.NH. 0218 0 C H.011Hzl (7) 1- (stearoyloxyethyl aminoethylimidazoline %NCH2 H. O

NO H2 7 V 2H,.NH. ozmNno o 011E" 1-stearamidoethylaminoethyltmidaaoline N-CH H. 0

N-CH2 zmmointnno 0.011} V 312H2s V f (9) 1- (N-dodecyl) -acetamidoethylaminoethylimidazoline N on om CnHsr-C NCHCH: (10) 2-heptadecyl,4,5-dimethylimidazoline N CH: Eli-0 \NOH2 CsH12.NH. 0121126 (11) l-dodecylaminohexylimidazoline NCH N-CHa GH11.NH.C2HI.OCIIHII 12 1-stearoyloxyethylamlnohexylimidazoline V aaraaaaa 4-methyl,2-d0decyl,l-methylaminoethylamlnoethyl tetrahydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula:

Such compounds, can, be, derived, of course, from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and higher homologuesa The substituents may vary dependingonthe source of the hydrocarbon radical, such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or the like. The group introduced may or may not contain. avhydroxyl radical as in the case of hydroxyacetic. acid,.acetic acid, ricinoleictacid, oleic acid, etc.

One advantage of a. two-ring, compound resides in the fact that primary-amino groupswhich constitute the terminal radicals of the parent polyamine, whether a polyethylene amine or polypropyleneamine, are converted so as to eliminate the presence of such primary amino radicals. Thus, the two-membered ring compound meets the previous specification in regard to the nitrogen-containing radicals.

Another procedure to form a two-membered ring compound is to use a dibasic acid. Suitable compounds are described, for example, in aforementioned U. S. Patent No. 2,194,419, dated March 19, 1940, to Chwala:

iniwhich Rrepresents a. small: alkyl" radical such; as methyl, ethyl, propyl, etc., andrnrepresentsa:small wholenumber greater than unity such as 2,.3-or 4. Substituted imidazoline can only be formed from that part of the polyamine which has a primary amino group present. There is no objection to the presence-of'atertiary amino radical as previously pointed. out. Suchderivatives, provided there is more than one secondary amino radical present in the ring compound, may bereacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as.to:convert one or more amino; nitrogenradicals into the.correspondinghydroxy alkyl radical, provided, how.- ever,,, that thereis. still a residue secondaryamine group. Fen instance, in the preceding formula if. n: represents; 4 it v means the-ring- .compound: would have: two secondary nitrogenradicals. and could be treated with asinglemole of; analkylene oxide and still provide: a satisfactory reactant for: the-herein; described condensation reaction.

Ring; comp:ounds,, such. as substituted.imidazolines, may be reacted with; a substantial amount of alkylene oxide asr-noted inthe; preceding paragraph and then a: secondary amino groupintroduced by twotstepsg first, reactionawith an'ethyIene-imine, and second, reactionwithanother moleof the oxide, or with an; alky-lating agent such. as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic, acid, an, alkyl bromide, etc.

As, to-oxyalkylated.imidazolines and a variety of suitable high molecularweight carboxy acids which may be the source of a substituent radical, see U. S. Patent No. 2,468,180, dated April 26, 1949, to-De Groote and Keiser.

Other suitable means may: be employed to eliminate a terminal primary amino radical. If there is additionally a basic-secondary amino, radical present then. the primary amino radicalcan be.subjectedito-acylation notwithstand: ing the fact that the surviving amino group has no significant basicity. As a rule acylation takes place at the terminal primary amino group rather than at the secondary amino group, thus one can employ a compound such as /N--QHQ: CflHar-C N-GH,

C2H4.NH.C2H4.NH2 2-heptadecyl,1-diet1:ylenediaminoimidazoline and subject it to acylation so as to obtain, for example, acetylated 2 heptadecyl, 1- diethylenediaminoimidazoline Similarly, a compound having no basic secondary amino radical but a basic primary amino radical can be reacted with amole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as N-CH& Ci'lHat-C N-OHa 1H4.NHQ

2-heptadecyl,l-aminoethylimidazollne which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of 2-heptadecyl,l-amino-ethylimidazoline, which can be' illustrated by the following formula:

NCH' C|7HuC N-CH:

Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, Z-heptadecyl,l-amino-ethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amino group. If ethylene imine is employed, the net result is simply to convert 2-heptadecy1,l-aminoethylimidazoline into Z-heptadecyl,l-diethylene-diaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group between nitrogen atoms. v

A more satisfactory reactant is to employ one obtained by the reaction of epichlorohydrin on a secondary alkyl amine, such as the following compound;

If a mole of Z-heptadecyl, l-aminoethylimidazoline is reacted with a mole of the compound just described, to

the resultant compound has a basic secondary amino group and a basic tertiary amino group. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

For purpose, of convenience, what has been said by direct reference is largely by way of illustration in which there is present 'a sizable sydrophobe group, for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups, etc. etc.

As has been pointed out, one can obtain all these comparable derivatives from low molal acids, such as acetic, propionic, butyric, valeric, etc. Similarly, one can employ hydroxy acids such as glycolic acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe effect as, for example, acids prepared by the oxyethylation of a low molal alcohol, such as methyl, ethyl, propyl, or the like, to produce compounds of the formula in which R is a low molal'group, such as methyl, ethyl or propyl, and n is a whole number varyingfrom one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloroacetic acid, followed by saponification'so'as toyield compounds of the type R(OCHzCH2)nOCH2COOH in which 7 n. has its prior significance. Another procedure is to convert the compound into a halide ether such as in R(OCHzCH2)nCl in which n has its prior significance, and then react such halide ether with sodium cyanide so as to give the corresponding nitrile R(OCH3CH3)nCN, which can be converted into the corresponding acid, of the following composition R(O CH2CH2),;COOH. Such acids can also be used to produce acyl derivatives of the kind previously described in which acetic acid isused as an acylating agent. v

What has'been said above is intended to emphasize the '16 fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and those which have a minimum hydrophobe property.

Examples of decreased hydrophobe character are exemplified by 2-methylimidazoline, 2-propylimidazoline, and Z-butylimidazoline, of the following structures:

H- CH) CzHr-G N-CHg H NCH| C 4119. C

N- H; I! (19) PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself. I A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at C. A suitable solvent is usually benzene, Xylene, or a comparable petroleumhydrocarbon or a mixture of such or'similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a Way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycoh One can also use a mixture of benzene or Xylene and such oxygenated solvents. Note that the use of 'such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, para-formaldehyde can be used but it is more diificult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected may be water-insoluble or water-dispersible, or water-soluble, or close to being Water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage formore than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refiuxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde'is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde 'but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low tem perature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to l0-24 hours, we then complete the reaction by raising the temperature up to 150 C., 'or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of'the resin based on'the molecular Weight of the-resin molecule, 2 moles ofthe'second'ary polyamine and 2 moles of'for'maldehyde. In someinstances we have added a trace of .caus'tic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of the nitrogen compound, and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular Weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparationof the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei ex cluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin .so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 35 C. and 612 grams of 2-oleylirnidazolinc, previously :shown in a structural formula as ring compound (3), were added. The mixture was stirred vigor- 'ously and'formaldehyde added slowly. In this-particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The Y residual xylene was permitted to stay in the cogeneri c mixture. A small amount of the sample was heated on a waterbath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6hours. v 7

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded'a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE It waist 20 PART The preparation of oxyalkylated derivatives of products of the kind which appear as examples in Part 4 is carried out by procedures and in apparatus which are substantially conventional for oxyalkylatiomand which will be illustrated by the following examples. In preparing the products of the examples, a conventional autoclave with required accessories for oxyalkylation having a capacity of about 25 gallons is used.

Example 1c The oxyalkylation-susceptible compound employed is the one previously described and designated as Example lb. Condensate 1b was in turn obtained from 2-oleylimidazoline and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 15.18 pounds of this resin condensate were dissolved in 6 pounds of solvent (xylene) along with 1.0 pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to'operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about to pounds. In some subsequent examples pressures up to pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for 15 minutes or longer, a total time of one hour. The reaction went readily, and, as a matter of fact, the oxide was taken up almost immediately. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 15.18 pounds. This represented a molal ratio of 34.5 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 3036. A comparatively small sample, less than grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was Strength of Reac- Reae- Max. Ex. Rosin Amt., Amine used Amt. of formaldehyde Solvent used tion tion distill. N 0 used grs. amine, and-amt. snd'amt. temp time tem grams P 0. (hrs.)

612 37%, 162 g.-. Xylene. 600 g. 30 148 306 37%, 81 g. Xylene, 450 g. 24 145 306 do. Xylene, 600 g. 28 150 281 30%, g-.. Xylene, 400 g. 28 148 281 'do. Xylene, 450 g 30 148 281 37%, 81 g Xylene, 600 g 26 146 394 d Xvlene, 400 g. 26 147 Xvlene, 450 g.... 26 146 Xylene, 600 g. 38 150 Xylene. 450 36 149 Xylene, g 21-22 24 142 379 do Xylene. 650 gm. 20-21 26 145 395 38%, 8l-g. Xylene, 425 g 2228 28 146 395 37%, 81 g Xylene, 450 g... 23-30 27 395 do Xylene, 550 g..- 20-24 29 147 Xylene, 440 g. 20-21 30 148 Xylene, 480 g. 21-26 32 146 Xylene. 600 g 2123 26 147 Xylene, 500 g 21-32 29 150 .do 21-30 32 150 Xylene, 550 g 21-23 37 150 Xylene, 440 g- 20-22 30 150 126 do Xylene, 600 g.. 2 -25 36 149 126 30%, 50 Xylene, 400 g 20-24 32 152 V The amlnenumbers referred torare the ring compounds identified previously; by numberv lAPart 3.

21 so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabularform in subsequent Tables Ill and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end. of each step and continuedoxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and sub jected to oxyalkylation with a difierent oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 111, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), to wit, 15.18 pounds. The amount of oxide present in the initial step was 15.18 pounds, the amount of catalyst remained the same, to wit, 1.0 pound, and the amount of solvent remained the same. The amount of oxide added was another 15.18 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 30.36 pounds and the molal ratio of ethylene oxide to resin condensate was 69.0 to 1.0. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 20 to 25 pounds. The time period was one and one-half hours.

Example 3c The oxyalkylation proceeded in the same manner described in Examples and 20. There was no added solvent and no added catalyst. The oxide added was 15.18 pounds and the total oxide at the end of the oxyethylation step was 45.54 pounds. The molal ratio of oxide to condensate was 103.5 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Example 10 and 2c. The-time period was somewhat longer than in previous examples, to wit, 3 hours.

Example 40 The oxyethylation was continued and the amount. of oxide added again was 15.18 pounds. There wasno added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 6072. The molal ratio of oxide to condensate was 138.0 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 3% hours. The reaction unquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another 15.18 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 9108 and the molal ratio of oxide to resin condensate was 172.5 to 1. The time period, however, dropped. to 3 hours.. Operating temperature and pressure remained the same as in the previous example.

Example. 6c.

The same procedure was followed as in the previous examples. The amount of oxide added was another 15.18 pounds, bringing the total oxide introduced to 91.08 pounds. The temperature and pressure during this period were the same as before.- There was no added solvent. The time period was 3 /2 hours. Molal ratio of oxide to resin condensate was 207.0 to one.

Example 7c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 106.26 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 12,144. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 121.44 pounds. The theoretical molecular weight was 13,662. The molal ratio of oxide to resin condensate was 276.0 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous ex-. amples and the time required for oxyethylation was 4 hours. i

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III, IV, V .and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in alS-gallon autoclave and then transferred to a ZS-gallon autoclave. vThis is immaterial but happened to be a matter of convenience only. The solvent used in all caseswas xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be note that compounds 10, through 400 were obtained by the use of ethylene oxide, whereas 410 through 80e.,were obtained by the use of propylene oxide alone.

Thus, in reference to Table In it is to be noted as follows:

The example number of each compound the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column;

Assuming that ethylene oxide alone is employed, as happens to be the case in Examples 1c through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusivelythe 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed. I

The 15th column shows the theoretical molecular weight at the end of the oxyalkylation period.

is indicated in eases 22-3 The 8th column states-theamount of condensate present in the reaction mass. at the end of the period.

As pointed "outpr'e'viou'sly, in this "particular series the amount of ireactionu'n'ass .withdrawnfor' examination was so small .th'atit' was ignored and 'for"this".reason' "the resincondensate in column 8 coincides with thefigure in column, 3.

'Column 9 showsthe amountof ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignoredinsofar that no propylene oxide was employed.

:5. Column 11 showszthe catalysttattthe .end ofsthe-reaction period.

=.-2Column.d2--.shows;"tha amountfofisolvent at the end of 'the 'rea'ction'period.

.-.:Golumri:13- shows. the; molalzratio of ethylene. .oxide'to condensate.

Column x14: can the; ignoredfifor other reason i that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 2c, 30, etc.

The second" column gives the maximum temperature employed during the'-oxyalkylation step-and "the third column'gives the maximum pressure.

'The'fourth column gives the time period employed.

' Then-as: 'three' columnsshow solubility tests by shaking a 'small'a'm'ount of"thecompoun'd,' including the solvent"p'resent, Wlth' several volumes of water,"xylene and kerosene. "It sometimes happens that although xylene in comparatively small amounts will dissolve in the'concentrated'material"When'the "concentrated material in turn is diluted with xylene separation takes place.

Referringto TableIV, Examples" 41c 'throu'gh 80c are the'counterpart's of Examples lcthrough 40c;exceptthat the oxide employed is propylene oxide insteadof ethylene oxide. Therefore, as explained previously, two columns ardblank, towit, columns 4'and 9.

"Reference is now made" to Table V. It .is to be noted these'compounds'are'designated by"dnumbers, 1d, 2d, 3d,'"etc.-, through and including 32d. They are derived, in turn-from com ounds in the "c series, for example, 360, 40c, 54c, and 760. "These compounds involve the use of both ethylene "oxide and propylene oxide. Since com ounds lc'through 400 were obtained'bythe use of ethylen'e'oxidait is obvious that those obtained from 36c and 40c, involve the use bf-"ethylene' oxidefirs't, and propylene oxide afterward. Inversely; those compounds obtained from 540 and 760 obviously come from a prior seriesin'which' propylene oxide was used first.

In the preparation of this series indicated by the small letter "d, as "1d; 2d, 3d,etc.,theinitial series such a s*3'6c, 40c, 54c, and 760, were duplicated and'the oxyalkylation stopped at the point designated instead of be ing carried further'asmay have been the case in theoriginal oxyalkylation step. Then oxyalkylation' proceeded by using the'second oxide as' indicated by the previous explanation, to"wit, propyleneoxide'in 1d through 16d; and ethylene oxide in 17d through 32d,=inclusive.

In examining the table beginning'with' 11!, it will be noted that'the initial product, i. e.,"36c, consisted of the reaction product involving 15.18 pounds of the resin condensate, 22.27 pounds 'ofeth'ylene' oxide, 1.0 pound of 'caustic'soda,'and 6.0 pounds of the solvent.

It is to be noted that referenceto the'catalyst"in"Table V'r'eferstothetotal'amount of catalyst, i. e.,"the catalyst present from thefirst'oxyalkylation step plusaddedcata 24 lystf iii-any. The "same is true' in-"regard "tonne :s'olvent. Referencetoithe s'olve'nt'refers to the totalsolvent present, i. e.,. that .from thefirst oxyalkylatiom'step plushdded solvent; if any.

In this series, it will be noted thatthe' theoretical molecular. weights-are: given prior to the oxyalkylation step and after v the oxyalkylation .step, although the value. at.the end-of-endstep istheatalue at theheginning .ofthe, next stop, except *obviouslynat .the: vory & start zthe..value de pends on the theoretical molecular weight at the end of the initial oxyalkylation: step;.i...e., oxyethylation for 1d through 16d and oxypropylation for 17d through 32d.

It'will'be noted:alsof thatnnder. the molaleratio-gthe :vlalues of both oxides to.theresincondensatc; are included.

T he- "datagiven :in regard to :the operating: conditions issubstantially the same as beforeJand-appears in iliable VIII.

The-productsresulting 'from'theseproceduresmaycon tain'rnodest amounts; or have small amounts; ofthe solventsasindicated'bythe figures in thetables. If desired the solvent-may be "removed by distillation, and particularly vacuum'distillation. Such distillation also mayremovetracesor .small amounts of uncombined oxide, if present and volatile. under thev conditions employed.

:Obviously,-in .the-use of ethylene oxide and propylene oxide in combination-one need not first :use one oxide and then the other, but one can mix the two oxides andJthus obtain. what:may.be :termed :anindiiierent oxyalkylation, i: 6.,2110; attempt to selectively. addaone. andithenstheother, or any other variant.

Needless to say, one could start with ethylene oxide and then use propyleneoxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, .and then go back. to propylene oxide; or, .one could-use a combination in which .butylene oxide is usedalong with either one of thetwo oxides justmentioned, or a combination ofboth of them.

The colors of theproducts usually vary from a reddish amber tintzto a definitely red, and amber. :The reasonis primarily that-no.effort=is.made to obtain colorlessresins initially. and .theresins themselves. may .be yellow,- amber, or even darkamber. -,Condensation of a nitrogenous :product invariably yields a darker product than.thez:o riginal resin and usually has a reddish color. The solvent employed, if xylene, addsnothing'tothe color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yieldlighter colored products and the more "oxide employedthe lightenthe color of-the product. Pfoductscan be prepared 'inwhich the final color is a lighter amber with a reddish tint. Suchproducts can bedecolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses'there is no 'justification for the-cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is'somewhatJmore. difiicult than ordinarily inthe case for the'reason that if one addshydrochloric acid,- for'exam-' ple, to "neutralize'the alkalinity one may, partially neutialize the basic nitrogen radical also. "The preferred procedure is "toignore' the presence of "the alkali unless it is objectionableor elseadd a stoichiometric amount io'fcon I centrated' hydrochloric" acid equal to the caustic soda present.

Mniec. wt. :based oreticai svalue alkyl Molal ratio oxide zoxide on thealkyl.

8888888&77777W|778752075374193827 7 6666666633333333 135780213660370 .A 11 A to oxyto oxy- Sol- Ethyl. l-"roni. vent, lbs.

-- snscept; suscept.

Composition at end mfim LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL W w, i L 987654 0 64210822222222 6666666 Didi 517.395 9 35729022222222 3333333 m b 7 5m2 0 7 5Q5 7 &O &0 &5 1RWSBRWRWRURWRWQQQQQQQQ X1 1233467 13466790000000033332333 P0 i i i 11111111 i 1 650665566222222226369258198764208 33333333777777778741963151735790 t 0 0 0 000 QQQOQQQQQQ9- 59QQ$Q752QiQhmL 33333333666666 6 123 45 1234679 a cmpd.,

' lbs.

888 888 866 66 8 .1 1 mmmmmmmmPiwwimmwmmwlwmm TABLE V E 501- 7 went, lbs.

lyst, 7 lbs.

00000055333338885555555500000555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Ethi. Prop]v Cataoxide lbs.

Composition before lbq.

Ex. No.

Kerosene Solubility Xylene Water TABLE VI Time;

hrs.

1%Ins01i1b]e Max. pres., p. s. i.

Max. temp., C.

"Oxyalkylation-susceptible.

Ex. N 0.

greases TABLE VIOontlnued Solubility Time,

hrs.

Xylene Kerosene Soluble. Insoluble.

Do. Insoluble.

Do. Dlsperslble. Soluble.

o. Dlsperslble. Soluble.

o. Dlsperslble. Soluble.

PART 6 The resin condensates which are employed as inter mediate reactants are strongly basic. Initial oxyalkyla= tion of these products with a monoepoxide or diepoxide either one can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 5 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be sufiicient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then. employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst-s may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble catalyst such as clay or specially prepared mineral catalysts have been used. If

for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenatedsolvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. It the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If

70 the product is going to be subjected to oxyalkylation subsequently, then the solvent'should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instancebut, everything else being equal, the solvent chosen should be the most economical one.

Example la The product was obtained by reaction between the diepoxide previously described as diepoxide A and oxyalkylated resin condensate 2c. Oxyalkylated condensate 2c has been described in previous Part 5 and was obtained by the oxyethylation of condensate 1b. The preparation of condensate 1b was described in Part 4, preceding. 'Details have been included in regard to both steps. Con- 32 amine the physical, properties. The material was an amvber,..or lightleddishamber, viscous, liquid. ,It wasinsoluble.in water; it was insoluble in gluconic acid, but it was solublejnxylene and, particularly in a mixture of 80% xylene and 20% -methanol. However, if-the material was dissolved in an oxygenated'solvent and then shaken with 5% gluconicacid it showed a .definitetendency to .disperse, suspend, -0? form a sol. and particularly in. a xylene-methanol-mixed solvent as :previously described,

densate in turn. s ed from amine 3 audiesin .10 with-"or. without the further addition of a little acetone.

2a. As previously pointed out amine 3 is Z-oIeylimidazoline. (See Part 5.) Resin 2a was obtained from paratertiarybutylphenol and formaldehyde.

In any event, 455 grams of the oxyalkylated resin condensate previously identified as 2c were dissolved injgapproximately an equal weight of xylene. About 4.2:grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 4.7 grams. ;l8.5

Generallyspeakingythe solubility.of these derivatives Y is in'linewith expectations by merely examining the solu- ---soluble-or even kerosene-soluble'due to high stage oxy-' bilitypoftahe; precedingintermediates, to Wit,.,the oxyalkylated resin condensates prior to: treatment with the di- 15 @pox'ide. These materials, of course, vary from extremely water soluble products due to substantial :oxyethylation, j to' those which conversely are water-insoluble-but xylene- ;propylation. Reactions with diepoxides. or polyepoxides grams of diepoxide A were mixed with an equal Weight: of .of the kind herein described reduce'the hydrophilepropxylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass: to about 109 C. The diepoxide was added slowly over a period of minutes. During this time the temperature 'erties.andiincreasethe hydrophobeproperties, i. e, generally make the-productsmorersoluble in kerosene or a mixture 'Of kerosene and xylene, or in xylene, .but less -soluble-in water. Since this is a general rule which apwas allowed to rise to about C. The mixture was 25 'plies' throughout, forsake of brevity future reference to allowed to reflux at about C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the refiuxing 'temperature rose gradually to about 175 C. The mixture the end of this period the xylene which had been removed by means of the phase-separating trap was returned 1 to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to exsolubility will be omitted. fjf"The procedureemployed, of :course, is simple in light ---of what hasbeen s'aidpreviously'and in effect is a procewas refluxed at this temperature for about 6 hours. .At .30 -methylglycide asoxyalkylating agents.

j duresimilar tothat employed 'in..the use of glycide or See,-for example, "Part Let U." S;'Patent No. 2,602,062, dated.July 1, 1952,

* to 'De Groote.

Tf'Various examples-obtained insubstantially thehsame mannerare enumerated'in the following-tables:

TABLE VII Ex. Oxy. Amt., Diep- Amt, Catalyst Xy Molar Time of Max. No. resin congrs. oxide grs. (NaOCHQ, lene, ratio reaction, -temp., Color and physical state densate used -grs. -grs. hrs. 0.

455 A 18. 5 4. 7 --474 2:1 6 175 Reddish -ember resinous mass. 304 A 9. 3 3.1 "313 2:1 6 175 D0. 387 A 9. 3 4. 0 396 2: 1 6 D0. 355 A 18.5 3.7 374 2:1 6 V 174 D0. 232 A 18.5 2.5 251 2:1 5.5 180 D0. 304 A 18. 5 3. 2 323 2:1 6 170 Do. 464 A 18. 5 4. 8 483 2: 1 6 172 Do. 355 A 18. 5 3. 7 374 2: 1 6 174 Do. 232 A 18. 5 2. 5 251 2:1 5 180 Do. 463 A .2185 i.-4.8 482 2:1 6 175 Do. v1 266 LA 9:3 .28 275 2:1 5 175 D0. ,342 A 9.3 8. 5 351 2:1 5 170 Do. 418 A I 9.3 I 4.3 427 2:1 6 168 D0. 266 A 9.3 v2.8 275 2:1 5 175 Do. 121 A 1.9 1.2 123 2:1 5 177 D0.

TABLE VIII Ex. Oxy. Amt, Diep- Amt Catalyst Xy- Molar Time of Max. No. resin con- ,grs. oxide .grs. (N20011:), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. 0.

4.55 p B 11 4.7 466 2:1 6 180 .Reddishemberresinous mass. 304 B 5.5 3.1 310 2:1 5 182 D0. 387 B 5.5 3.9 393 2:1 5 'Do. 355 f B 11 3.7 366 2:1 5 185 Do. "232 B 11 2. 4 243 2:1 5 184 D0. 304 B 11 .,3.2 315 2:1 5 182 D0. 464 i B 11 l 4.8 475 2:1 6 180 .DO. 355 Q B 11 3.7 1866 2:1 6 185 DO. .232 'B U 11 2.4 -'243 2:1 5 180 .Do. 463 B '11 4.7 474 2:1 6 178 Do. 266 B .15 2.7 272 2:1 4.5 185 Do. .3342 ..B -..5.5 3.5 348 2:1 5 .185 jDo. -418 B '5. 5 '4. 2 424 2:1 5. 5 184 D0. 266 5 B 5.5 2.7 272 2:1 4.5 185 Do. 121 B 1.1 .1. 2 122 2:1 4 185 .-D0.

TABLE IX Prob. moi. Ex. N0. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product 9, 480 4, 740 2, 370 12, 510 2, 502 1. 051 15, 830 3, 166 1, 583 7, 470 3, 735 1, 868 5, 000 5, 000 2. 500 6. 440 3, 220 l, 610 9, 650 4, S 2, 413 7, 470 3, 735 1. 868 5, 000 5, 000 2, 500 9, 630 4, 815 2, 408 11, 000 2, 200 1, 100 14, 030 2, 806 1. 403 17, 070 3, 414 1,707 11, 000 2, 200 l, 100 24,660 2, 466 1, 233

TABLE X Prob. moi. Fx. No Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio as in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amountof initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Aminewfl wxyalkylated ResirOCHflAmine) in which D. G. E. represents a diglycidyl ether as specified.

As has been pointed out previously, the condensation 34 reaction may produce other products, including, for example, a product which may be indicated thus in light of what has been said previously:

[ (Amine) CH2(Resin) This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated (Amine) CH2 (Resiu)] When a diglycidyl ether is employed one would obviously obtain compounds in which two molecules of the kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

Oxyalkylated(Amine)CHAResin) L l Likewise, it is obvious that the two different types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

l(Amine)(JHz(Oxyalkylated Resin)CHi(Amine:

| .Oxyalkylated(An1ine)CHz(Resin) 0 xyalkylated (Amine) CH2 (Amine) I iil . I l'" Oxyalkylated(Amine)CHz(Amine) Actually, the product obtained by reaction with a diglycidyl ether could show considerably greater complexity due to the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 7 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929. dated January 7, 1953, to De Groote, and particularly to Part Three. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 42, herein described.

Having thusdescribed our invention what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water=in-oil-type characterized by subjecting. the emulsion 'tothe action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water insoluble, low stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over'6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-f ormingreactivity; said resin being derived by reaction between a .difunctional mono- 'hydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula tuted in the 2,4,6 position; (b) cyclic ar'nidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is preseat at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and

' (c) formaldehyde; said condensation reaction being conducted at a temperature sufirciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the res inous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate With nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings isfree from any radical having more than 4 uninterrupted carbon atoms in asingle chain; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl polyepoxides (BB) be memhers of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of theclass of solvent-solubleliquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 rnoles of the 'oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide. I

:2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide;'said first manufacturing step being ame th'od of '(A) .condensing (a) an oxyalkylation susceptible, "fusible, nonoxygenated organic'solvent-soluble, water-insoluble, lowhydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctionai phenols; said phenol being of the formula 7 in which is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and

(0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta a-lkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyallcylated resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is freefrom any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more 20 carbon atoms; with the further proviso that said reactive monoepoxidederived compounds (AA) and non- ;aryl polyepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a'rnethod of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl hydrophile diepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the diepoxide, is water-soluble; said diepoxide being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxide being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl diepoxides (BB) be members of the class consisting of nonthermosetting organic solvent-soluble liquids and lowmelting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl diepoxide.

4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being ob tained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation-snsceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corre sponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula 4 in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with a hydrcxylated diepoxypolyglycerol having not more than 20 carbon atoms; with the further proviso that said monoepoxide-derived compounds (AA) and said hydroxylated diepoxyglycerol (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the hydrcxylated diepoxyglycerol.

6. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei.

7. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted.

8. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde.

10. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin is not over 5.

11. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said 3-9 xyleneisolution is shaken vigorously with -1 to 3 volumes of Water. V 7 v 13. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

14. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene'are sufficient to produce an e' sion When said xylene solution is shaken vigorously with l to 3 volumes of water. 7 a

15. The process ofclaim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are suliicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

16. The process of claim 6 With the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

17. The process of claim 7 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting jof (a) the anhydro base as is (b) the free 'b'ase,-i,andq(c-) the salt of gluconic acid, inanequal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim. 8 with the proviso that the hydrophile properties of the .product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

19. The process of claim 9 with the proviso that the hydrophile propertiesof the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sutficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water. p

20. The process of claim 10 with the proviso that'the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; AND FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AND OXYLKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER - INSOLUBLE, LOW- STAGE PHENOL-ALKEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAI PHENOL BEING OF THE FORMULA 